Esters of endoethylene-substituted cyclopentanols



Patented Sept. 2, 1947 results or sNnoErmENa-sunsrrrru'mn crcLornn'rmoLs. V v

Herman A Bruson, Philadelphia, 2a., assi nor to i 1 The ltesinous Products: Chemical Company, v f I 'lhiladelphiagl'a a corporation of No Drawing. Application use a. 1944,

i a serum. 539,593 2 1 This invention relates ment products of organic carboxylic acids and adducts of cyclopentadiene with mono-oleflnic,

compounds having at least threecarbon atoms,

said products being esters of. an endoethylenesubstituted cyclopentanol. I

In co-pending application, Serial No. 476,639, filed February 20, 1943, which issued on February 26, 1946, as United States Patent No. 2,395,452, it is shown that adducts of cyclopentadiene with itself, such as dicyclopentadiene, tricyclopentadiene, and 'tetracyclopentadiene, add organic carboxylic acids in the presence of acidic catalysts to form addition-rearrangement products which are esters or a new ring system termed the nordicyclopentadiehe or norpoly cyclopentadiene ring system.

In accordance with the present invention,

which is a continuation-impart of co-pending application Serial No. 531,763, filed April 19, 1944,

which issued on August '7, 1945, as United States.

Patent No. 2,381,433, adducts of cyclopentadiene with mono-olefinic compounds having at leastthree carbon atoms in the molecule are reacted with organic carboxylic acids in the presence of acidic condensing agents to form addition products which are rearranged esters of endoethylene-substituted cyclopentanols, which may be considered closely related to the above-mentioned norcyclopentadiene ring systems. 1 t

A typical illustration is the reaction of an acid, R-COOH, with the cyclopentadiene-styrene adduct. r

The product formed by the molecular additionrearrangement is very probably that represented by (A) although formula (B) is also a possibility.

Thus far it has not been possible to decide-defl-- nltely between the two. In any event, the prodto additlon-rearrange "Fromm. (61.260-487) uct is not a; simple"- addition side of the double bond andotH to'the-fother. Similar considerations' apply to all-th'e freactions herein set forth;

The aboveproducts are defined by the empirical formula RCQQCrHmlCaHc' 7 wherein C"zH 1qrepresents, the, rearranged cycles from the adduct, from cyclopentadiene and styrene and R represents the residue of a c arboxvylic acid, RCOOH. Inplace of the -,C H5 group, which specifically here results from styrene as a component, there may occur the non-oleflni c portion orresidue obtained when one of the-other mono-oleflnic compounds recited below-is added to cyclopentadiene.- If R represents this residue,

4 the formula may then be written a I Rcoocmmrv p "In the case of awpolycarboxylic acid, -cneor morermolecules of an adduct of cyclopentadiene and a mono-olefinic compound of at least three carbon atoms maybe reactedwith each molecule of the acid. vIn some cases mixtures 0f esters are frequently formed. For xample, oxalic acid, may

' react with one or with two molecules cl an adduct to form a half-ester and a. dl-ester, RQCOCOOH and, ROCOCOpR, respectively.

Various adducts of cyclopentadiene with monoolefiniccompounds having three or more carbon atoms in the molecule can be used for the purpose of this invention. These comprisethe socompounds, such as coumarone. safrol CH2=' -VCH"CHP3, cyclopentene called Diels-Alder" type of adducts of cyclopentadiene with unsaturated hydrocarbons such as propylene, flcyclopentene, styrene, indene, allylbenzene, and thelike; these also comprise, the adducts of cyclopentadien with unsaturatedalcohols, esters, halides, or ketones, forexample, allyl alcohol, crotonyl alcohol, allyl chloride, allyl benzoate, allyl acetate, allyl o l eate,.yiny thyl ketoneyvinyl acetate, vinyl ben zoatean Other adducts of cyclopentadiene-with iejetic and with allyl or crotonyl ethers, f

benzyl allyl ether, phenylallyl ethr octyl-y allyl ether and the like, mayalsobe used. t

The adducts of cyclopentadiene with nn-- saturated hydrocarbons recited above}? prpnylene,

Jail-CH C? H:

- Y. e ,CHz=CI-I-CoHis,indene v I such -'as stannic chlori I and allyl benzene, CH2=CH-CI-I2CaH, or the other adducts which are shown, may be termed to either the 2-position or the 5-position. The

due from the above hydrocarbons, -CI-Is,- i

CaHs, .--CsH5, C7Hs', and CH2Co H5, re:- spectively, which are represented by Rfin the general formula given above.

In practicing this invention, it has been found that a wide variety of organic carboxylic acids containing one 7 or more 7 carboxyl groups may be employed. -These may be aliphatic,,arylaliphatic, cycloali-phatic, aromatic, hydroaromatic, or heterocyclic, and may be saturated or unsaturatedin' character. -It has also been established thatthe organic non-carboxyl portion of the reacting carboxylic acid compound may contain a wide variety of groups or substituents, for example, halogen, cyano, thiocyanoj nitro, keto or acyl, mercapto,

' ether, acy oxy. a koxy. aryloxy, carbalkoxy, hy-

droxy or other relatively inert radicals.

'It should be noted at this point that, inthe case of carboxylicacids having free hydroxyl or mercapto groups, excess cycopentadiene-olefine the free hydroxvl or mercapto group occurs in addition to esterification of the free carboxyl group. Typical useful organic carboxylic acids for the purpose of this invention are the following:

Formic, acetic. propionic. butyric, isobutyric,

- valeric, capric, 2-ethyl butyric, 2 ethy1 hexoic,

lauric, palmitic, stearic, oleic, linoleic, linolenic, ricinoleic, elaeostearic, licanic, abietic,'-glycollic,

lactic, alpha-hydroxyisobutyric, chloroacetic, di-

chloroacetic, trichloroacetic, beta-cbloropropi-- onic, alpha 'chloroprc pionic, thioglycollic, acrylic,

crotonic, alpha-methyl acrylic, "ethox'yacetic,

, adduct may be necessary since etherification of I by Bryant-0 62115.

or other oxygenated organic compounds include-- ing ketones, alcohols, esters, fiuoboric acid, dihydroxyiluoboric acid, sulfuric acid, acid esters of sulfuric acid such as ethyl acid sulfatefsulfonic acids such as benzene fonicacid and other strongly acidic materials e, aluminum chloride. boron chloride, and the like.

'of' these' variou catalysts, boron trifiuoride I and its coordinationcomplexes, particularly those with ethers and carboxylic 'acidsare preferred.

As examples of-the coordination complexes, there may be cited those with diethyl ether and with dibutyl ether, exemplified .by BFa-O(C2Ht)2 and BF3'O(C4H9)2; with. acetic or chloroacetic acid typified by BFa-2CHaCOOH orBF32C1CH2CO0H,

and with water which complex may be representsulfonic acid or butyl su1- pentanol was obtained as ed by the formula BFsKHzO): where ai is two.

The quantity of active catalyst employed may one or .be varied over a wide range. poodresults have been obtained with as little as two per cent of -50", C. to about 140 0. although both higher (e. g.,

150200 C.) or lower temperatures, even room I -tem rature, ca. in man cases be used. Inert adduct is substituted with the non-o1efinic'resin y organic solvents such as dioxane, ethylene dichloride, or dibutyl ether may be used, if desired, to

was stirred at C. for four hours. The product was cooled, washed with water, then with dilute soda solution, dried, and distilled in vacuo.

The acetate of endoethylene-phenylcyclopenta- 1101 having the probable formula distilled over at -135 C./1-2 mm. as a colorless oil in a yield of 1'1 grams. Upon redistillation'the pure compound boiled at l28-130 C./1 mm. The above compound may also be formulated CHaCOO-CvHrwCsHs, wherein C7H1o is the endoethylene cyclopentylene group.

Example 2 A mixture consisting of 2 g. of 50% sulfuric acid, 46 g. of 87% formic acid, and 17 g. of cyclopentadiene-styrene adduct was stirred four hours at 95 C. and worked up as in Example 1.

The formate of endoethylene-phenylcycloe a colorless oil havin a boiling point of 118-120 C./1.5 mm. The prod uct has the formula HCOO'C'IHIOC8H5, wherein C-1H1o is the endoethylene cyclopentylene group.

' Example. 3

A mixture consisting of 0.1 g. of 98% sulfuric acid, 9.5 g. of monochloroacetic acid, and 17 g. of cyclopentadiene-styrene adduct was reacted and worked up as in Example 1 to yield the chloroacetate of endoethylene-phenylcyclopentano1 as a colorless oil boiling at 16'l-170 C./2 mm. having the probable formula llalJ C i v I asa'avac 5 The product may also be given the formula CICHQCOO'C'IHM'CGHS, wherein 01310 is endoethylene cyclopentylene group.-

Example 4' A mixture of 2 g. of BF3'O(C4He):, 12.2 g. of-

benzoic acid,-and 17 g. of cyclopentadiene-styrene adduct was stirred for flve hours at 95 C. and

worked up as in Example 1.

. The benzoate of endo'ethylene-phenyl cyclopentanol distilled over at 200-210 C./1-2 mm. as a, viscous, colorless oil. i

Example 5 A mixture of 0.5 g. of Bra-moans) a, 9 g. of crotonic acid, and 17 g. of 'cyclopentadienestyrene adduct was stirred for five hours at 95 C. and worked up as in Example 1.

The crotonate of endoethylene-phenylcyclopentanol distilled over at 160165 C./1.5 mm. as a faintly yellow thick oil.

Example 6 A mixture of 5 g. of 40% sulfuric acid, 120 g. of glacial acetic acid, and 62.5 g. of the adduct of cyclopentadiene with vinyl acetate on C(l on, H!

n H-ooocm .was stirred at 95 C. for four hours. The product was cooled, washed .twice with water, dried and distilled in vacuo to yield 41 g. of the diacetate of endoethylene hydroxycyclopentanol as a colorless oil boiling at 142-145 C. at 14 mm. having the probable formula A mixture of 5 g. of 40% sulfuric acid, 120 g. of aiacial acetic acid, and 83 g. of the adduct of cyclopentadiene with allyl acetate a E-CHg-OCOCH:

was stirred for five hou'rs at 95 C. and worked up as in Example 6.

The diacctate of the endoethylehe-hydroxymethylene cyclopentanol distilled over at 134- 136 C./ mm. asa colorless oil having the probable formula v on Cgl CHe H; ore-ooon-I-- CH:--OCOCHa The yield amounted to 75 grams and possessed the following constants: I

Upon hydrolysis with alcoholic sodium hydroxide solution, it yielded the corresponding eudoeththe ylenehydroxymethylene' cyclopentanol as a colorless oil boiling at 150-155 C./ 6 mm. Example 8;

A mixture of a g. of glycolic acid, so 3. of cvcylopentadiene-indene adduct (1,4-endomethylene-tetrahydro-fluorene) p and 5 g. of BF3-O(C2H5)a was stirred at 9095 C. for six hours. The product was cooled, washed with dilute sodium carbonate solution and then with water, dried, and distilled in vacuo to yield the glycolate of endoethylene-hydroxycyclopentanoindane having the probable formula I as a colorless balsam boiling at 185 C./1 mm.

' Example 9 i mixture of 32 g. of 85% lactic acid, 5 g. of

98% sulfuric acid, and 54 g. of cyclopentadieneindene adduct was stirred at C. for six hours and worked up as in Example 8.

The lactate of endoethylene-hydroxy-cyclopentanoindane obtained is a viscous oil boiling at -180 C./0.5-1 mm.

In the same manner, any of the other types of carboxylic acids enumerated herein may be used, the products in every case being esters of endoethylene-substituted cyclopentanol derivatives,

ment product of acetic acid and cyclopentadi enestyrene adduct, said product being an acetate of endoethylene-phenylcyclopentanol CI IsCOO C'ZHIDCGHB wherein C'zHm is the endoethylene cyclopentylene group.

3. As a new compound, an addition-rearrangement product of -ch1croacetic acid and cyclepentadiene-styrene adduct, said product being a chloroacetate of endoethylene-phenylcyclo pentanol, ClCHzCOO-C I-Im-Cslis, wherein C'rHm is the endoethylene cyclopentylene group,

4. As a new compound, an addition-rearrangement product of formic acid and cyclopentadienestyrene adduct, said product being a formate of endoethvlene-phenylcyclopentanol wherein C'IHIO is the endoethylene cyclopentylene I group.

5. A method of preparing esters of endoeth-'- yiene-substituted cyclopentanols whichcomprises reacting in the presence 01' an acidic condensing agent an aliphatic monocarboxylic acid of one to eighteen carbon atoms and an adduct of one 5 mole of cyclopentadiene and one mole ofa hydrocarbon selected from a member of the class consisting of propylene, cyclopentene, styrene, and allylbenzene, whereby there occurs an addition reaction together with a. molecular rearrangement of the cyclic system of said adduct.

6. The method of claim 5 wherein the acidic I condensingagent is a sulfuric acid catalyst.

7. The method of claim 5 wherein the acidic condensing agent is a boron trifiuoride catalyst.

HERMAN A. BRUSON;

8 Bummer-2s 'crrnn The following reierences are of record in the file of this patent: I UNITED STATES PATENTS Number Name Date 1,838,465 Stephan et al. Dec. 29, 1931 1,755,750.. Stephan ct a1 Apr. 22, 1930 Bruson Aug. 7, 1945 OTHER REFERENCES (I) Nametkin et al., Ber. Deut. Chem. vol."6 1 B (II) Nametkin et al., Comptes Rendus 'Acad. Sci. U. R. S. S. vol. 36 (1942) pp. 142-144 (Avail. Dept. of Agri. Lib.) Q I 

